Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
  • C08G18/4027—Mixtures of compounds of group C08G18/54 with other macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
  • C08G18/168—Organic compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/54—Polycondensates of aldehydes
  • C08G18/542—Polycondensates of aldehydes with phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0041—Foam properties having specified density
  • C08G2110/005—< 50kg/m3
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2115/00—Oligomerisation
  • C08G2115/06—Oligomerisation to carbodiimide or uretone-imine groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2150/00—Compositions for coatings
  • C08G2150/60—Compositions for foaming; Foamed or intumescent coatings

Definitions

• This invention relates to a polyurethane-polycarbodiimide foam such that it is unnecessary to use fluorine-containing halogenated hydrocarbons as a blowing agent and blowing on the spot is possible using a spray blowing machine or the like.
• the object of this invention is to provide a process for preparation of a polyurethane foam such that it is unnecessary to use fluorine-containing halogenated hydrocarbons as a blowing agent and blowing on the spot is possible, without any problem, using a spray blowing machine.
• a benzylic ether type phenol resin containing hydroxymethyl groups (1) reacts with an organic isocyanate (2) in the presence of an organotin catalyst for urethane formation to generate carbon dioxide gas (for example, refer to "Hybrid Phenolic/Urethane Foams" Anthony J. PaPa and Frank E. Critchfield, Union Carbide Corporation Technical Center, South Charleston, W. Va. 25303), and have tried to use a benzylic ether type phenol resin containing hydroxymethyl groups as a polyol component for formation of polyurethane foams.
• blowing is insufficient by only carbon dioxide gas generated by the reaction of the hydroxymethyl groups of the benzylic ether type phenol resin with the organic isocyanate, and a desired foam of a low density (high extent of foaming) cannot be obtained.
• a process for preparation of a polyurethane-polycarbodiimide foam which comprises reacting a polyol component containing a benzylic ether type phenol resin having hydroxymethyl groups with an organic polyisocyanate component in the presence of an organotin catalyst for urethane formation and a carbodiimidating catalyst.
• the characteristic of this invention lies in using a benzylic ether type phenol resin having hydroxymethyl groups as at least part of the polyol component, and therein the "benzylic ether type phenol resin having hydroxymethyl groups" is a kind of phenol resin obtained by reacting phenol with formaldehyde at a temperature of 100 to 130°C using a catalyst comprising a salt of a divalent metal with naphthenic acid, carboxylic acid or the like, its properties and state can be changed, depending on polymerization conditions, in a range from viscous liquid, through semi-solid, to solid, and it can be prepared, for example, according to a process disclosed in U.S. Patent No. 3,485,797.
• the benzylic ether type phenol resin used in this invention liquid one is especially suitable.
• Such a benzylic ether type phenol resin containing hydroxymethyl groups can contain hydroxyl groups derived from the hydroxymethyl groups in a range of generally 300 to 700 mg KOH/g, preferably 450 to 600 mg KOH/g in terms of a hydroxyl value.
• the benzylic ether type phenol resin containing hydroxymethyl groups can be used alone as the polyol component in this invention, when it is used alone, the curing rate gets too fast and cracks, etc. are liable to occur in the inside of the formed foam, and therefore, it is preferable, in general, to use it together with other polyols.
• polyols usable together those which have so far been used in preparation of polyurethanes are usable, and there can, for example, be mentioned dihydric alcohols such as ethylene glycol, diethylene glycol, neopentene glycol, 1,4-butanediol, 1-6-hexanediol and 1,4-cyclohexanedimethanol; trihydric or higher alcohols such as glycerol, trimethylolpropane, tris(2-hydroxyethyl) isocyanurate and pentaerythritol; or polyester polyols, polyether polyols, etc. obtained using them. These other polyols can be used alone or in combination of two or more.
• dihydric alcohols such as ethylene glycol, diethylene glycol, neopentene glycol, 1,4-butanediol, 1-6-hexanediol and 1,4-cyclohexanedimethanol
• phthalic ester polyols particularly suitable are phthalic ester polyols, ethereal Mannich polyols and ethereal ehtylenediamine polyols having a hydroxyl value in the range of generally 50 to 800 mg KOH/g, particularly 100 to 500 mg KOH/g.
• the use amount of the benzylic ether type phenol resin containing hydroxymethyl groups is not strictly limited and can be widely varied depending on physical properties desired for the foam to be formed, the kind of other polyols to be used together, etc., but is suitably in the range of usually 5 to 100 wt.%, particularly 30 to 80 wt.% based on the total amount of the polyols.
• organic polyisocyanate component to be reacted with the polyol components there can be used an aliphatic, alicyclic, aromatic, aromatic-aliphatic or another polyisocyanate compound containing two or more isocyanato groups (NCO) in one molecule, and as example thereof there can be mentioned aromatic polyisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4-toluene diisocyanate with 2,6-toluene diisocyanate, crude toluene diisocyanate, methylenediphenyl diisocyanate polymethylenepolyphenylenepolyisocyanate (crude MDI), and 4,4',4''-triphenylmethylene triisocyanate; aliphatic polyisocyanates such as hexamethylene-1,6-diisocyanate and lysine diisocyanate methyl este
• the suitable use ratio of the organic polyisocyanate component to the polyol component is in the range of generally 1 to 4, particularly 1.1 to 3.0 in terms of the NCO/OH equivalent ratio.
• an organotin catalyst for urethane formation and a carbodiimidating catalyst are used together as the reaction catalysts.
• the organotin catalysts for urethane formation there can, likewise, be used those generally used in reactions for urethane formation, and as examples thereof there can be mentioned dibutyltin dilaurate, dibutyltin diacetate, dibutyltindialkyl maleate, tin stearate, tin octanoate, etc.
• the use amount of the organotin catalyst for urethane formation is not particularly limited, but suitably in the range of usually 0.1 to 14 wt.%, particularly 2 to 9 wt.% based on the total amount of the polyols used.
• tertiary amine catalysts such triethylenediamine, 2-methyltriethylenediamine, bis-2-dimethylaminoethyl eher, N,N', N''-trimethylaminoethylethanolamine, N,N-dimethylaminoethylmorpholine, 1-isobutyl-2-methylimidazole, 1,8-diazabicyclo(5.4.0)undecene-7 and 1,5-diazabicyclo(4.3.0)-nonene-5 and their derivatives; salts of these tertiary amine catalysts with acids such as carboxylic acids; organomethallic salt catalysts such as cobalt naphthenate, tetra(2-ethylhexyl) titanate, ferric 2-
• trimerizing catalysts there can, for example, be mentioned tertiary amine catalysts such as N,N',N''-tris(dimethylaminopropyl)hexahydro-S-triazine and 2,4,6-tris(dimethylaminomethyl)phenol; organometallic salt catalysts such as potassium acetate, potassium octanoate, potassium 2-ethylhexanoate, sodium carbonate and iron oxalate; etc.
• trimerizing catalysts can be used in the range of generally 0 to 10 wt.%, particularly 0.1 to 2 wt.% based on the total amount of the polyol components to be used.
• the carbodiimidating catalyst to be used together there can be used a catalyst known as one catalyzing carbodiimidation reaction as shown in the above reaction formula B, and as examples thereof there can be mentioned organic phosphorous compounds such as triphenylphosphorene oxide, hexamethylenephosphonamide, dilaurylphpsphonamide, triethyl phosphate, triallyl phosphate, 1-phenyl-3-methyl phosphate and 1-phenyl-3-methylphosphorene oxide; trizaine ring-containing tertiary amine compounds such as 1,3,5-tris(N,N-dialkylaminoalkyl)-S-hexahydrotriazine derivatives; organometallic compounds such as titanium tetrapropoxide and zirconia tetrapropoxide; etc., and among them 1-phenyl-3-methyl-1-phosphorene oxide is preferred.
• organic phosphorous compounds such as triphenylphosphorene oxide, hexamethylenephosphonamide,
• the use amount of such a carbodiimidating catalyst is not strictly limited, either, but, in general, it is suitable that the use amount is in the range of 0.05 to 4 wt.%, particularly 0.1 to 2 wt.% based on the organic polyisocyanate to be used.
• water it is desirable, in some case, to use water as a blowing auxiliary.
• water when its use amount is too large, the resultant foam tends to get brittle, and therefore, in general, it is preferred to use water in an amount of 0.1 to 4 wt.%, particularly 0.5 to 2 wt.% based on the organic polyisocyanate.
• foam stabilizers such as ethylene oxide or propylene oxide adducts of dimethylsilicon, nonionic surfactants and anionic surfactants
• flame retardants such as tris(2,3-dibromopropyl) phosphate, tris(2-chloroethyl) phosphate, tris( ⁇ -chloropropyl) phosphate and trimethyl phosphate
• viscosity-reducing agents such as dibutyl phosphate, dioctyl phosphate and polypropylene carbonate
• fillers such as antimony trioxide, zeolite and hazilite
• coloring agents such as pigments and dyes; etc.
• a process for preparing a polyurethane-polycarbodiimide foam using the above various components there can, for example, be exemplified a process which comprises preparing a polyol composition in advance by mixing all the components other than the organic polyisocyanate component, adding the organic polyisocyanate component to this polyol composition and mixing the mixture, pouring it into a mold or spraying (e.g. by a spray blowing machine) it on the surface of a base material, and then blowing and curing it.
• Time required for the blowing and curing is usually on the order of 5 to 30 seconds.
• the extent of foaming of the formed foam can be regulated freely, and for example, it is possible to prepare a foam having an extent of foaming as large as its free foaming density being 18 to 40 kg/m3, particularly 20 to 30 kg/m3.
• polyurethane-polycarbodiimide foams prepared by the process of this invention are improved in physical properties such as the lowness of adhesive property and brittleness which have come into problems in usual foams by water blowing.
• a foam having a large extent of foaming in usual water blowing the viscosity of the stock solution gets high and thus it is necessary to mix large amounts of a flame retardant and a viscosity-reducing agent at the time of spray blowing, whereas according to the process of this invention, it is possible to prepare a stock solution of 300 to 500 c.p. easily only by mixing a flame retardant in an amount of the order of 10 %.
• Benzylic ether type phenol resin having hydroxymethyl groups (hydroxyl value: 596 mg KOH/g; BEP-1000 produced by HOTOGAYA CHEMICAL CO., LTD.) 10 g Phthalic ester polyol (hydroxyl value: 210 mg KOH/g; PL-135 produced by Tohorika Co., Ltd.) 4 g Organotin catalyst for urethane formation (dibutyltindialkyl maleate salt; T-52NJ produced by Katsuta Kako Co., Ltd.) 0.5 g Catalyst for urethane formation (salt of triethylenediamine with carboxylic acid; DABCO 8154 produced by Sankyo Air Products Co., Ltd.) 1.5 g Trimerizing catalyst [2,4,6-tris (dimethylaminomethyl)phenol; TMR-30 produced by Sankyo Air Products Co., Ltd.] 2 g Carbodiimidating catalyst (1-phenyl-3-methyl-1-phosphorene oxide; 33 %
• Example 2 For comparison, the same operations as in Example 1 were made using each component of the same composition as in Example 1 and compounding rates shown in the following Table 2 to prepare foams.
• the cream time, rise time, density and the state of foams thereof are shown in Table 2.
• Table 2 Comparative example 1 2 3 4 Crude MDI 50 50 50 50 50 50 Benzylic ether type phenol resin 10 10 10 - Polyol PL-135 4 4 4 14 Catalyst for urethane formation 1 1 1 1 1 1 Trimerizing catalyst 2 2 2 2 2 2 2 2 2 2 Organotin catalyst for urethane formation - 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Carbodiimidating catalyst 0.5 - - 0.5 Foam stabilizer 1 1 1 1 Flame retardant 6 6.5 6 5.5 Water 0.5 - 0.5 0.5 Cream time (sec) 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Rise time (sec) 17 15 9 14
• Example 3 The same operations as in Example 1 were made except that the benzylic ether type phenol resin, the catalyst for urethane formation, the trimerizing catalyst and the organotin catalyst among the components of Example 1 were replaced by components shown in the following Table 3, whereby foams were prepared.
• the cream time, rise time, density and the state of foams thereof are shown in Table 3.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)

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Citations (5)

• 1992
  • 1992-09-29 JP JP28229392A patent/JP3178916B2/ja not_active Expired - Fee Related
• 1993
  • 1993-09-28 CA CA002107138A patent/CA2107138A1/en not_active Abandoned
  • 1993-09-29 DE DE69317498T patent/DE69317498T2/de not_active Expired - Fee Related
  • 1993-09-29 EP EP93115720A patent/EP0590638B1/de not_active Expired - Lifetime
• 1996
  • 1996-03-18 US US08/617,430 patent/US5621051A/en not_active Expired - Fee Related

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